Mono-t-butylxylene by alkylation



l Aug. 2o, 1957 Original Filed. Qct. ,26, 1953 United States Patent O `MONO-T-BUTYLXYLENE BY ALKYLATION David A. McCaulay, Chicago, Ill., and Arthur P. Lien, Highland, Ind., assignors to Standard Oil Company, Chicago, Ill., a corporation of Indiana Original application October 26, 1953, Serial No. 388,238,

now Patent No. 2,766,307, dated October 9, 1956. Divided and this application February 21, 1956, Serial No. 566,808

This invention relates to the preparation of monoalkylxylenes by the reaction of an olen and xylene. More particularly, the invention relates to the preparation of ethylxylenes. Still more particularly the invention relates to the preparation of the symmetrical 1,3,5-ethylxylene.

This application is a division of our cpending application Serial No. 388,238, led October 26, 1953, now U. S. Patent No. 2,766,307.

'Ihe commercial polystyrene resins have the disability of a softening point lower than the boiling point of water. It is known that resins prepared from dimethylstyrene have a softening point higher than the boiling point of water. Ethylxylenes with an ortho arrangement of a methyl and the ethyl group dehydrogenate to methylindenes, which are very diicult to separate from the dimethylstyrene. The methylindenes act as plasticizers and lower the softening point of the polydimethylstyrene; the presence of more than about 6% of these contaminants lowers the softening point of the resin below the boiling point of water. In the prior art processes, this undesirable ortho relationship between a methyl and the alkyl group exists in the major portion of the ethylxylene product.

The development of the hydroperoxide synthesis for phenols has caused a large demand for substituted secondary alkylbenzenes. Essentially pure isomers are desired in order to permit the production of phenols of specic characteristics. 1,3,5-isopropylxylene is of particular interest in this synthesis.

Itis an object of this invention to alkylate xylenes with olens to produce preferentially monoalkylxylenes, which contain predominantly 1,3 dimethyl alkylbenzene. Another object of our invention is to produce ethylxylenes containing a predominant amount of 1,3,5-ethylxylene by ethylating xylenes. Still another object is to prepare essentially pure 1,3,5-ethylxylene by ethylating xylenes. A further object is the preparation of 1,3,5-secondary alkylxylenes by alkylating xylene. A particular object is the preparation of 1,3,5-isopropylxylene. Yet another object is the preparation of 1,3,5-tert-butylxylene. Other objects will be apparent in the detailed description.

It has been found that by the use of liquid HF--BFa catalyst under controlled conditions, each of the xylene isomers or mixtures thereof can be readily alkylated with ethylene, propylene, butene-l, butene-2 and isobutylene to produce preferentially monoalkylxylenes.

The feed to the process comprises any one of the three xylene isomers or mixtures thereof. In the presence of HF--BFa agent, olens alkylate benzene and toluene very readily; therefore, the presence of more than appreciable amounts of benzene and toluene should be avoided.

The acid phase can dissolve a fair amount of parains, for example, the xylene feed may contain as much as 3 volume percent of parafms without forming a separate hydrocarbon phase (when at least about l mol of- BFa is present per mol of xylene charged). The presence of a hydrocarbon phase, i. e., ralnate phase, is not desirable because some of the xylene is withdrawn from the acid phase and the yield'of alkylxylene is decreased and the product distribution is shifted from the desired maximum of 1,3,5-alkylxylene.

Under the conditions of the process, ethylbenzene is rapidly converted to mainly triethylbenzene, ethylxylene, and dialkylethylbenzene. These products boil well above the desired monoalkylxylene and may be separated therefrom by distillation. When the olefin used is ethylene, it may be possible to tolerate large amounts of ethylbenzene in the feed; a suitable feed is the Cs aromatic hydrocarbon fraction obtained by extractive distillation of hydroformate or platformate, i. e., naphtha obtained by the catalytic reforming of virgin naphtha in the presence of hydrogen, which fraction contains about 2-3% of paraflns and slight amounts of olelins and Cs` aromatic hydrocarbons.

Liquid xylenes react with BF3 and liquid HF to form a complex containing 1 mol of BFs per mol of xylene and also, probably, 1 mol of HF per mol of xylene. Alkylxylenes also form a complex with BFa and HF. These complexes are very soluble in liquid HF. It is necessary in the process that sufficient liquid HF be present to dissolve all the complex formed. The presence of liquid HF in excess of this amount is desirable. Thus the amount of liquid HF should be between about 3 mols per mol of xylene present in the feed and about 50 mols. It is preferred to use between about 5 and 20 mols of liquid HF. Put in 'another way, the amount of liquid HF used may be between about to about 400 volume percent based on xylene charged.

The process must be carried out under substantially anhydrous conditions. stantially anhydrous, that is, the liquid HF should not contain more than about 2-3% of water.

The amount of BFs used in the process may range from about 0.1 mols per mol of xylene (a catalytic amount) to about 5 or more mols. When a mixture of alkylxylene isomers is a satisfactory product, at least about 0.4 mols of BFs` per mol of `xylene charged should be used.

In order to obtain better yields of alkylate and to obl tain a better alkylate product distribution, the process should be operated under conditions wherein essentially all the feed is dissolved into the acid phase.4 Some BFa and HF may exist in a separate gaseous phase, but it is preferred to operate at a pressure high enough to dissolve essentiallyl all the BFa in the acid phase. This essentially single homogeneous phase may be obtained by using at least about 1 mol of BFs per mol of xylene charged, for example, 0.9 mol.

The production of the desired 1,3,5-alkylxylene is favored by the use of enough BFa to complex all the xylene in the feed. Thus, it is preferred to use between at least 1 and about 3 mols of BFS per mol of xylene charged, for example, 1.5 mols.

The` alkylation of xylene with olen, in the presence of HF-BFa agent, produces a mixture containing xylene,

The liquid HF used must be subt alkylxylene and polyalkylxylene. The polyalkylate yield may be reduced Abymoperating with -an .excess `of xylene over the amount of olen charged. The mol ratio of xylene to olefin should be at least l and a ratio of 20 or more may be used.

With ethylene, it is preferred to use a mol ratio between about 2 and 5, when operating at ordinary atmospheric temperatures, i. e., between about and about +30 C. At higher temperatures, for example, -1-60 C., the mol ratio may be only slightly in excess of l, for example, 1.03.

The distribution of alkylxylene isomers and the ,relative yields of the various alkylate products is dependent upon both the temperature andthe time ofcontacting. It is believed that a mixture ofisomersis obtained-when the olefin adds to the xylene to f or-m-alkylxylene. Following th@ alkyltn felion,angiallgrilation reaction occurs in which the 1,3,5-alkylxylene is preferentially formed. Under suitable Conditions Lof time and temperature, essentially all the alkylxylene r ent in the acid phase will be the l,3,5-,isomer. Shorter ntaoting times may be used when a high p urity ;1, 3,v5,all y lxylene,l i. e., about V95%, product fraction isidesired.

The permissible temperatures vary markedly with `the type of olefin used in the process. The oleiins usable in the process are selected from theclass consisting of ethylene, propylene, isobutylene, `butene-l and butene-Z. The use ofpentenes and higher olens results in excessive side reactions, such as cracking and rearrangement of the alkyl group. In order to setrout lthe relationship of temperature and time to product distribution, the various olefms are discussed in accordance with the individual characteristics of the alkylate products.

Ethylene alkylqtion The .ethylxylenes undergo cracking reactions and the formation of tars, condensed ring compounds and gases at temperatures above about |l35 C. Xylenes undergo a disproportionation reaction at high temperatures. In order to minimize the loss of xylene to trimethylbenzene, the ethylation process should be carried out at -a temperature of not more than about +75 C. and preferably below about +65 C. v

Low temperatures reduce the rate of formation of 1,3,5-ethylxy1ene and also affect the rate o f alkylation. In general, the contacting time, at a particular temperature, is dependent upon the desired degree of conversion of the ethylxylene fraction to the V1,13,5 e t l41ylxylen,e isomer. Temperatures as low as 20 C. or lower can be used if the correspondingly longer .time Lof contacting is tolerable; for example, at -,-20 C., a time of 20 hours should be used. At about +35 C., a suitable reaction time is about 5 minutes. When using higher ratios of xylene to ethylene, the preferred temperature is between` about and |35 C., using a time between about 5 minutes and 5 hours, the longer times corresponding to the lower temperatures. Higher temperatures, i. e., -1-50 to +65 C., have a favorable effect on the yield of ethylxylene at lower xylene to ethylene ratios. Essentially pure 1,3,5-ethylxylene can be produced in very high yield by carrying out the ethylation at about -}-.65 C. for a time of about 10 minutes; at about -l-.50J C., a suitable `time is about minutes.

In general, it is preferred to operate with about the minimum contacting time needed to obtain the degree of 1,3,5-ethylxylene readily obtainable at the particular temperature of operation.

Propylene, butene-l and butene-Z qlkylation The alkylation of xylene with olens from the class consisting of propylene, butene-l and butene-Z gives products containing a secondary alkyl group, namely, isopropyl and sec-butyl. These secondary alkylxylenes undergo extensive cracking reactions at temperatures above about +80 C. Condensation reactions proceed to an appreciable extent when long contacting times are used .4 at temperatures of about +40 C. and higher; it is desirable to operate at a temperature-ofnot more-than'about +40 C.

The secondary alkylxylenes isomerize much more readily than the ethylxylenes; therefore, very low temperatures, such as 20 C., may be employed without having to use extremely long contacting times. At 20 C., high purity 1,3,5-secondary alkylxylene is obtained when using a time of about 2 hours.

As the temperature is raised, the time of contacting is correspondingly decreased. When the temperature of contacting is about |-20 C., the contacting time is between about 5 and 20 minutes. At a temperature of +40 C., the time is between about l and 5 minutes; at

these higher temperatures, the time of contacting shouldv be as short as practicable in order to decrease the yield of side reaction products, i. e., the time should be Yas close to about 1 minute as equipment limitations will permit.

It is preferred to operate the secondary alkylxylene production process at a temperature between about-0 and +20 C. for a time between about 5 and about 60 minutes, the longer times corresponding to the lower temperatures.

Isobutylene alkylation The alkylation of xylene-with isobutylene gives prod# ucts containing a tertiary butyl group.l 'These tert-butylxylenes undergo extensive cracking and condensation reactions at temperatures of about |25 C. In order to substantially avoid these side-reactions, kthe temperature of operation should `be maintained below about -i-l5' C. The yield of the desired 1,3,5-tert-butylxylene isimproved by operation at temperatures of not more than about 0 C., for example, 20 C. The tert-butyl group is so acitve that temperatures as low as about 75 C. may be used without requiring extremely long contacting times.

When operating at a temperature of about +15 '.C., very short contacting Vtimes Vshould be used-between about l minute and 5 minutes. At-0 C., the contacting time may be between about 5 and 30 minutes; The lower the temperature of contacting, the longer the permissible contacting time, without signilicant adverse effect on the yield of the 1,3,5-tert-butylxylene.

EXAMPLES The results obtained by the invention are Villustrated by several experimental examples yand one using HF alone as the catalyst. The results of these experiments are presented in Tables I and II. In order .to illustrate the experimental procedure, `runs -5 and 7 are set yout in .detail which amounted to an uncorrected EP3/xylene ratio of.

1.5. At the reaction temperature of +20 C., the pressure in the reactor was p. s. i. a. Taking into account the Vfree space in the reactor, the partial pressure of HF and the solubility of BFa at this temperature and pressure, i

the free BFa was calculated to be about 1.5 mols. 'Ihus the corrected BFS/xylene was 1.0, i. e., the theoretical for the complexing of all. the meta-xylene.

Ethylene gas was added to the contents of the reactor over a period of 5 minutes; 1.21 mols were added for a xylene/ethylene ratio of 2.50. The pressure on the reactor indicated the ethylene was rapidly absorbed. The reactor contents were maintained at 20 C. for 15 minutes. The contents were withdrawn into a Dry-Ice cooled ask containing about 70 ml. of water. determined by visual observation, onlyone single phase homogeneous system had existed in the reactor.

Insofar as couldl be TABLE I period vf 5 to the www m a Ethylene W38 added minutes; 1.18 mols were added for a total xylene/ethylene ratio of 2.57. The contents of the reactor were maintained at 25 C. for 4 hours. At the end of this time, the -contents of the reactor were Withdrawn into a -Dry- Ice cooled flask containing water. Visual observation of the contents as they were withdrawn indicated the existence of only a single phase homogeneous system.

The reactor contents were handled in the manner described in run 5. The total product .distribution in the 11111 WBS I Hydrocarbon Mols Percent 11i-xylene., u 1. 76 p-xylene 0. 26 1,3,5-ethylxylene 0. 72 72. 7 1,3,4-ethylxylenc Trace 1,3,2-ethylxylene Trace 1,4,3 ethylxylene 0.01 1. Cu aromatics 0. 26 26. 3

The properties of the total ethylxylene product in run 7 are:

' In Table I, run 1 shows the use of liquid HF as the catalyst for the ethylation of meta-xylene. In this run, 58% of the ethylene reacted to form aromatics containing three or four ethyl groups (C14 and Cre aromatics). Of the ethylxylene produced, almost `80% was 1,3,4- ethylxylene which has a methyl group and the ethyl group in ortho relation. Run 2 is substantially identical with run 1 except that 0.74 (corrected) mol of BFa was added per mol of xylene. In this run, no C16 aromatics were produced. The directional effect of the BFs on the ethylxylene distribution is shown by the fact that the desired 1,3,5-ethylxylene represents about 60% of the total ethylxylene as against about 5% in run 1.

Run 5 shows the remarkable improvement obtained in the yield of the desired 1,3,5-ethylxylene when the amount of BFa present is suicient to complex all the xylenes so as to form a single phase homogeneous system. This is particularly noteworthy in view of run 4 where the BFS was present in an amount only slightly under the theoretical amount; here the ethylxylenes contained about of 1,3,4-ethylxylene; this effect of the single phase homogeneous system is all the more striking since the amount of ethylxylene produced was about the same in each run.

Runs 6 and 7 used a mixed xylene feed. In run 6, the para-xylene alkylated to form the 1,4,3-ethylxylene isomer. The ethylbenzene in the feed alkylated to triethylbenzene rather than to diethylbenzene. In run 7, the 1,4,3-ethylxylene resulting from the ethylation of para-Xylene has been substantially completely isomerized to 1,3,5-ethylxylene; this result is believed to be primarily the etect of the single phase homogeneous system. In run 7, the high disappearance of para-xylene is due to isomerization to the meta isomer, in addition to ethylation.

Runs 9 and l0 illustrate the etect of high temperature operation on the direction of the ethylation. In runs 9 and 10, no detectable amounts of any ethylxylene isomer, other than the desired 1,3,5-isomer, were present. In run 9, 22% of the alkylate was made up of the diand tri-ethylxylenes; in this run, slightly less than an equimolar amount of xylene and ethylene was present. However, Ain run 1 0, wherein a slight excess of Xylene was present, only about 6% of the alkylate consists of the diand tri-ethylxylenes. These runs show the vmarked benecial effect on yield of the presence of even slight amounts of excess xylene when operating at higher ternperatures.

Run 1l illustrates the propylation of `rrr-xylene. The alkylate contained 81% of isopropylxylenefall of which was, within analytical error, the 1,3,5fisoprOpylXylQ1i1e isomer. The higher boiling fraction consisted of a wide boiling range mixture of alkylbenzenes and condensation products. y

Run l2 illustrates the isobutylation of m-xylene. in an appreciable yield of materials believed to be polyisobutylenes was formed which is not considered in the reaction product mixture reported. The identiliabrle alkylate consists of the 1,3,5-tert-butylxylene, Almost an equal quantity of alkylbenzenes and condensation products were formed. A shorter time would have increased the yield of the 1,3,5-tert-butylxylene.

ILLUSTRATIVE EMBODIMENT The accompanying drawing shows one embodiment of our process for the production of high purity 1,3,5-ethyl.- xylene by the ethylation of meta-xylene. It is'to be ,understood that this embodiment is shown for purposes of illustration only and that many other variations ot our process can be readily devised by those skilled in the art.

In this illustration, the charge consists of substantially pure meta-xylene from a source 11. However, the charge could be a mixture of meta-xylene, para-xylene and ethylbenzene, ortho-xylene or a mixture of meta, ortho?, paraxylene and ethylbenzene. Meta-xylene from source 11 is passed through line l12 into line 13. Liquid HF from source 14 is passed through valved line 16, through line 17, and through line 18 into line 13. The amount of liquid HF used here is 10 mols per mol based on xylene charged. BFs from source 19 is passed through valved line 21, through line 22 and into line 18 where it is co-mmingled with the liquid HF. The amount of BF3 used in this example is 1.5 mols of BFa per mol of xylene charged in order to insure the complexing of all xylene charged and the formation of a single phase homogeneous system. The liquid HF-f-BFg in line 18 joins the xylene in line 13 and the whole passes into mixer 23.

Mixer 23 may be any form of device that provides through agitation, for example, an `oriiice mixer. The reaction of the BFS, HF and meta-xylene to form the complex is exothermic and mixer 23 is provided with a cooling coil 24 to enable the temperature of the reaction mixture to be controlled.

Ethylene from source 25 is passed through valvedlline 26 into line 27 where it meets the homogeneous system passing out of mixer 23. The amount of ethylene used in this example is 1 mol per 2,5 mols of xylene. Reactor 2S is provided with a coil 29 which is used to maintain the temperature of the reaction mixture relatively constant. Temperature in the reactor in this example is about +20 C. The reactants are held in reactor 28 for a time suiicient to Aobtain ethylation and conversion of the ethylxylenes into the desired symmetrical 1,3,5-ethylxylene. In this example, the reaction time is 15 minutes.

From reactor 23, the homogeneous system is passed into line 3i) and on into cooler 31. Cooler 31 is needed only when very high reaction temperatures are used; the reaction mixture is cooled quickly in order to eliminate disproportionation of the xylene.

From cooler 31, the mixture is passed through line 32 into stripper 33. In stripper 33, the HF and BFS are removed from the hydrocarbons. In order to avoid the formation of undesirable products through disproportionation and cracking, the removal of the HF and BFa is carried out under vacuum; the stripping operation is facilitated by the use of a stripping agent; butane is introduced into stripper 33 through line 34.

The HF and BFa are passed out of stripper 33 through line 36, through vacuum pump 37 and line 38 into condenser 39. In condenser 3.9, the butane and HF are liquificd and are passed through line 41 into settler .42. The free BFa is passed out of settler 42 through lines 43 and 44 to line 22 for reuse in the process. The liquid butano is passed out of settler 42 through line 46 and may be returned to line 34 for reuse in the stripping operation.

The liquid HF, .saturated with BFS, is passed out of settler Here- 9 42 through valved line 47 into line 17 and may be reused in the process.

The hydrocarbons are passed out of stripper 33 through line 51 through heater 52 and line 53 into fractionator 54. Fractionator 54 is provided with a reboiler 55, which reboiler, in conjunction with heater 52, provides the heat necessary to separate the hydrocarbons into the respective fractions. The unreacted Xylene is taken overhead from fractionator 54 through line 56 and is condensed in cooler 57. The xylene is recycled to the reactor by way of valved line 58 and line 59 and line 12.

The ethylxylenes are withdrawn from an upper part of ractionator 54 by Way of line 61 and are passed to storage not shown. The ethylxylenes in this example consist of about 95% 1,3,5-ethylxylene and the remainder the 1,3,4- and 1,3,2-ethylxylene congurations.

The higher boiling C12 and any C14 aromatic fraction is Withdrawn from the bottom of fractionator S4 by Way of 'line 64 and are passed to storage, not shown.

One embodiment of the process has been described wherein substantially pure meta-xylene has been the feed material. A mixture of meta-Xylene, ortho-xylene and paraxylene can be used with only one variation from the above conditions. For the mixed xylene feed a reaction time of about 2 hours is used in order to isomerize the mixed ethylxylenes to the 1,3,5-ethylxylene.

When the feed to the process contains ethylbenzene, in addition to Xylenes, no change in operating conditions need be made. The ethylbenzene reacts to form triethylbenzene and ethylxylene. The triethylbenzene is passed out of the system with the higher boiling C12 and C14 fractions.

When no appreciable demand exists for by-product diethylxylene and triethylxylene, the process is carried out at higher temperatures. The Xylene to ethylene ratio is 1.1 and reactor 28 is maintained at +65 C.; the reaction time is 8 minutes. Essentially pure 1,3,5-ethylxylene is withdrawn by way of line 61. In this method of operation, about of the alkylate is the l,3 ,5-ethylxyleue.

Thus having described the invention, what is claimed is:

1. A process for the preparation of essentially pure 1,3,5-te1t-butylxylene, which process comprises, (l) cond tacting, under substantially anhydrous conditions, a feed consisting essentially of at least one Xylene isomer with at least about 1 mol of BFa and between about 3 and 50 mols of liquid HF, respectively, per mol of xylene in said feed, to form an essentially single phase homogeneous system, (2) adding isobutylene in a mol ratio of Xylene to isobutylene of at least about 1, while (3) maintaining the reaction zone at a temperature of not more than about -l- 15 C. for a time such that side reactions are minimized, (4) removing HF and BFa from a hydrocarbon product and (5) recovering from said product a tert-butylxylene fraction consisting essentially of 1,3,5-tert-buty1xylene.

2. The process of claim 1 wherein said temperature `is not more than about 0 C. and the time of contacting at a temperature of 0 C. is not more than about 30 minutes and wherein the lower the temperature the longer the permissible contacting time.

3. The process of claim 1 wherein said feed is p-xylene.

4. The process of claim 1 wherein said feed is o-xylene.

References Cited in the file of this patent UNITED STATES PATENTS 2,275,312 Tinker et al Mar. 3, 1942 2,423,470 Simons July 8, 1947 2,653,980 Condon Sept. 29, 1953 2,766,307 McCaulay et a1 Oct. 9, 1956 OTHER REFERENCES Nightingale et al.: Jour. Amer. Chem. Soc., vol. 64 (1942), pp. 1662-1665.

Nightingale et al.: Jour. Amer. Chem.. Soc., vol. 76 (November 1954), pp. 5767-5770. 

1. A PROCESS FOR THE PREPARATION OF ESSENTIALLY PURE 1,3,5-TERT-BUTYLXYLENE, WHICH PROCESS COMPRISES, (1) CONTACTING, UNDER SUBSTANTIALLY ANHYDROUS CONDITIONS, A FEED CONSISTING ESSENTIALLY OF AT LEAST ONE XYLENE ISOMER WITH AT LEAST ABOUT 1 MOL OF BF3 AND BETWEEN ABOUT 3 AND 50 MOLS OF LIQUID HF, RESPECTIVELY, PER MOL OF XYLENE IN SAID FEED, TO FORM AN ESSENTIALLY SINGLE PHASE HOMOGENEOUS SYSTEM, (2) ADDING ISOBUTYLENE IN A MOL RATIO OF XYLENE TO ISOBUTYLENE OF AT LEAST ABOUT 1, WHILE (3) MAINTAINING THE REACTION ZONE AT A TEMPERATURE OF NOT MORE THAN ABOUT +15* C. FOR A TIME SUCH THAT SIDE REACTIONS ARE MINIMIZED, (4) REMOVING HF AND BF3 FROM A HYDROCARBON PRODUCT AND (5) RECOVERING FROM SAID PRODUCT A TERT-BUTYLXYLENE FRACTION CONSISTING ESSENTIALLY OF 1,3,5-TERT-BUTYLXYLENE. 